CN1764350A - Method for removing resin mask layer and method for manufacturing solder bumped substrate - Google Patents

Method for removing resin mask layer and method for manufacturing solder bumped substrate Download PDF

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Publication number
CN1764350A
CN1764350A CNA2005101135083A CN200510113508A CN1764350A CN 1764350 A CN1764350 A CN 1764350A CN A2005101135083 A CNA2005101135083 A CN A2005101135083A CN 200510113508 A CN200510113508 A CN 200510113508A CN 1764350 A CN1764350 A CN 1764350A
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CN
China
Prior art keywords
mask layer
resin mask
substrate
scolding tin
photoresist
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Granted
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CNA2005101135083A
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Chinese (zh)
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CN100551207C (en
Inventor
樱井均
阿部公博
松本规雄
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Harima Chemical Inc
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Harima Chemical Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
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    • H01L24/11—Manufacturing methods
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3485—Applying solder paste, slurry or powder
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    • H01L2224/05573—Single external layer
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    • H01L2224/1147—Manufacturing methods using a lift-off mask
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    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/04—Soldering or other types of metallurgic bonding
    • H05K2203/043—Reflowing of solder coated conductors, not during connection of components, e.g. reflowing solder paste
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    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0562—Details of resist
    • H05K2203/0568—Resist used for applying paste, ink or powder
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    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
    • H05K2203/0769—Dissolving insulating materials, e.g. coatings, not used for developing resist after exposure

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Abstract

Using a dry film resist that is a photosensitive resin, a resin mask layer is formed around electrodes on a substrate. A solder precipitating composition is applied on the substrate, and this solder precipitating composition is heated to precipitate solder on the surface of the electrodes. Subsequently, in removing the resin mask layer, at least one selected from glycol ethers and aminoalcohols is used. Thereby, the resin mask layer is removed after heating process. This makes it possible to easily remove the heat-processed resin mask layer in a short period of time without damaging solder resist and solder bumps on the substrate.

Description

The manufacture method of the substrate of the method for removing of resin mask layer and tape welding tin projection
Technical field
The present invention relates to using precipitation type scolding tin composition when the electronic loop upper surface of base plate is installed electronic component, remove and use the resin mask method to form the manufacture method that scolding tin particularly forms the substrate of the method for the resin mask layer under the scolding tin projection situation and tape welding tin projection.
Background technology
In recent years, be accompanied by the miniaturization and of electronic instrument, the multitap thin spaceization of electronic component also in progress, for conductive pattern, and forms the fine pitchization of a plurality of conductors also in progress with minimum interval in narrow range.Therefore, engage with electronic component in order to make the electronic loop substrate, just extensively the installation method of employing use scolding tin projection replaces terminal conjunction method in the past.In addition, at the design aspect of wiring, also extensively adopt the through hole (via on pad) of what is called on pad at design through hole on the substrate.
As the method that forms the scolding tin projection, the common resin mask method that is to use the solder paste that has mixed soldering tin powder and flux that adopts.That is, resin mask method in the past is to form resin molding being provided with on the substrate of electrode, forms the peristome that electrode part is exposed by development treatment.Then, fill above-mentioned peristome, make the solder paste fusion form the scolding tin projection by heat treated with solder paste.Then, finally remove the resin mask layer.
But, in above-mentioned resin mask method, owing to carrying out heat treated (being generally more than 200 ℃),, be difficult to remove fully the resin mask layer so also improve the anti-fissility of resin mask layer by this heat treated in order to form the scolding tin projection for this reason.On the other hand, if the resin mask layer remains on the substrate, bring bad influence might for the installation of electronic component thereafter.
In addition, as the remover of resist, use strong alkali solution usually, when dipping substrate in such strong alkali solution, the scolder resist and the scolding tin projection of substrate have the possibility that sustains damage.So, also might have problems aspect the scolding tin connection reliability thereafter.
As the method for removing of resin mask layer, open the remover that records in the flat 7-288372 communique as the solvable type resist of alkali the spy and use organic base solution, particularly use monoethanolamine.Open in the flat 6-250403 communique the spy and to record:, use the strong alkaline aqueous solution that contains triethanolamine as the stripper of the plating resist that on substrate, forms by the water soluble corrosion resisting agent.But, peel off for the resist of in these communiques, putting down in writing, before stripping process, do not carry out high heat treated.So think that resist peels off also than being easier to.
Summary of the invention
Problem of the present invention is, provides not the scolder resist of substrate and scolding tin are caused damage and can simply remove the method for removing of resin mask layer of the resin mask layer that is heated processing and the manufacture method of circuit substrate at short notice.
The inventor etc. concentrate on studies in order to solve above-mentioned problem.Found that neodoxy as follows, promptly, forming on the electrode under the situation of scolding tin by the resin mask method, when the resin mask layer that uses after glycol ethers or alkamine are removed heat treated, can simply remove the resin mask layer that is difficult to peel off because of heat treated at short notice, and give the scolder resist of substrate or damage that the scolding tin projection causes few, so, the scolding tin connection reliability can be improved.
That is, the method for removing of the resin mask layer among the present invention comprises: use the dry film photoresist layer to form the operation of resin mask layer around electrode that the peristome from the insulating barrier that is formed at substrate surface exposes; The operation of coating precipitation type scolding tin composition on aforesaid substrate; This precipitation type scolding tin composition of heat treated and separate out the operation of scolding tin at above-mentioned electrode surface; With the operation of removing above-mentioned resin mask layer.The removing of above-mentioned resin mask layer after the heat treated can use at least a kind of selecting from glycol ethers and alkamine to carry out.
And then the manufacture method of the substrate of the tape welding tin projection among the present invention comprises: use the dry film photoresist layer to form the operation of resin mask layer around the electrode of substrate surface; The operation of coating precipitation type scolding tin composition on aforesaid substrate; This precipitation type scolding tin composition of heat treated and separate out the operation of scolding tin projection at above-mentioned electrode surface; With use at least a kind of from glycol ethers and alkamine, selecting and remove the operation of the above-mentioned resin mask layer after the heat treated.
The inventive method is effective especially more than 200 ℃ the time in the temperature of above-mentioned heat treated.In addition, when having the high vitrification point of temperature than above-mentioned heat treated at least 1 in the insulating barrier of substrate, because the substrate shape in the heat treated is fixed, so effective especially.
By the present invention, when on electrode, separating out scolding tin by the resin mask method, can form the resin mask simply with operation still less, and can simply remove resin mask layer after the heat treated at short notice, and give the scolder resist of substrate or damage that scolding tin causes few, thereby have the effect that can improve the scolding tin connection reliability.
Can clear and definite other purpose of the present invention and advantage by following explanation.
Description of drawings
Fig. 1 is the concise and to the point operation schematic diagram of an execution mode of expression the inventive method.
Embodiment
Below, the present invention will be described with reference to accompanying drawing.Fig. 1 is the simplified diagram of the method for removing of the resin mask layer in expression an embodiment of the invention.Shown in Fig. 1 (a), on the surface of substrate 1, form scolder resist film 3 (insulating barriers), expose electrode 2 from the peristome that forms at this scolder resist film 3.On the surface of this substrate 1, except the part of electrode 2, also forming resin mask layer 4 (is Ba Yan: dam).Then, shown in Fig. 1 (b), coating precipitation type scolding tin composition 5 on the surface of substrate 1, heating shown in Fig. 1 (c), separates out scolding tin on the surface of above-mentioned electrode 2, form scolding tin projection 6.Then, shown in Fig. 1 (d), remove resin mask layer 4, shown in Fig. 1 (e), as required, carry out equating (flattening).
Electrode 2 exposes with the spacing of regulation on the surface of substrate 1.Use resins such as epoxy system, acrylic acid series, polyimides system on scolder resist film 3, preferred epoxy is a resin.
From forming the viewpoint of homogeneous film thickness, in the resin material that forms resin mask layer 4, preferably use the photoresist of film like, more preferably dry film photoresist.In order to make projection, preferably has the dry film photoresist layer of the photo-sensitive resin of the thickness more than the 10 μ m, more than the preferred 30 μ m from the viewpoint of the scolding tin amount of separating out by separating out scolding tin.Also have, the thickness of photo-sensitive resin is preferably below the 300 μ m, below the preferred 150 μ m, if thickness surpasses 300 μ m, then is difficult to make it to be cured to the bottom of photo-sensitive resin.
The dry film photoresist layer is meant in support film (carrier film) and goes up stacked photoresist and on the surface of this photo-sensitive resin the face of support film opposition side (that is, with) 3 layers of stacked body of photoresist that protective film (cover film) forms are set.
The dry film photoresist layer of Shi Yonging in the present invention preferably has and contains photoresist that specific mix proportion forms as photo-sensitive resin.
Below the photoresist that is adapted at using among the present invention is described.
Photoresist among the present invention preferably contains: (A1) weight average molecular weight is 40,000～90,000 the alkali solubility macromolecule that contains carboxyl 15～35 quality %, (A2)) weight average molecular weight be 100,000～150,000 the alkali solubility macromolecule that contains carboxyl 15～35 quality %, (B) addition polymerization monomer 15～60 quality %, (C) Photoepolymerizationinitiater initiater 0.01～10 quality % and (D) weight average molecular weight be 1000～3000 PPOX 7～30 quality %.
From flexible viewpoint, (A1), the alkali solubility macromolecule optimal ethylene base co-polymer of (A2) composition.And then, from the viewpoint of development, preferred carboxylic ethylenic copolymer.Here, carboxylic ethylenic copolymer is to instigate from α, at least a kind the 1st monomer of selecting in the beta-unsaturated carboxylic acid, at least a kind the 2nd monomer of selecting compound, styrene and styrene derivative, (methyl) acrylonitrile and (methyl) glycidyl acrylate that is replaced by alkyl or alkoxyl with hydrogen on (methyl) alkyl acrylate, (methyl) acrylic acid hydroxyalkyl acrylate, (methyl) acrylamide and its nitrogen carries out the compound that ethylene copolymerization obtains.Also have, " (methyl) acrylate " is meant methacrylate or acrylate.
As the 1st monomer that in carboxylic ethylenic copolymer, uses, can enumerate acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester etc., can distinguish separately and use, also can be used in combination more than 2 kinds.
The ratio of the 1st monomer in carboxylic ethylenic copolymer is preferably 15～40 quality %, more preferably 20～35 quality %.In order to keep alkali-developable, the ratio of the 1st monomer is preferably more than the 15 quality %, and the viewpoint from the solubility of carboxylic ethylenic copolymer is preferably below the 40 quality %.
As the 2nd monomer that in carboxylic ethylenic copolymer, uses, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) cyclohexyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, many glycol monomethyls (methyl) acrylate, many propylene glycol list (methyl) acrylate, (methyl) acrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide, styrene, AMS, p-methylstyrene, to chlorostyrene, (methyl) acrylonitrile, (methyl) glycidyl acrylate etc., can distinguish separately and use, also can make up more than 2 kinds.
The ratio of the 2nd monomer in carboxylic ethylenic copolymer is preferably 60～85 quality %, more preferably 65～80 quality %.
From the viewpoint of the balance of fissility and scolding tin patience, carboxylic ethylenic copolymer preferably uses has different weight average molecular weight.And then it is 40,000～90,000 the alkali solubility macromolecule that contains carboxyl 15～35 quality % that photoresist preferably uses (Al) weight average molecular weight with photoresist gross mass benchmark, use (A2) weight average molecular weight with photoresist gross mass benchmark is 100,000～150,000 the alkali solubility macromolecule that contains carboxyl 15～35 quality %.
(B) composition can use known addition polymerization monomer.Oxyethylene modification many (methyl) acrylate etc. that for example can make up many oxyalkylenes list (methyl) acrylate, many oxyalkylenes two (methyl) acrylate, bisphenol-A oxyalkylene modification diacrylate, polyalcohol uses more than a kind or 2 kinds.Use level is preferably 15～60 quality % with the gross mass benchmark of photoresist, more preferably 20～50 quality %.For photo-sensitive resin fully being solidified and keeping intensity as resist, above-mentioned amount is preferably more than the 15 quality %.In addition, for the crack after preventing to solidify, the total content of above-mentioned addition polymerization monomer is preferably below the 60 quality %.
The two key concentration D of the addition polymerization of every 100g photoresist TBe preferably more than 0.07 from the adhering viewpoint of resin mask, be preferably below 0.12, more preferably 0.08～0.11 from the viewpoint of the resolving power of resin mask.That is, preferably with the two key concentration D of the addition polymerization of every 100g photoresist TBe that 0.07～0.12 photoresist is stacked on support film, use the dry film photoresist layer that protective film forms is set on the surface of this photo-sensitive resin forms the resin mask layer.
Obtain above-mentioned couple of key concentration D by following calculating formula T
1. be W in photoresist, containing addition polymerization monomer [1] 1Situation, calculate two key concentration D 1
D 1=(d 1/ M 1) (calculating formula a)
D 1: two key concentration of addition polymerization monomer [1]
d 1: the number with two keys of addition polymerization of 1 molecule addition polymerization monomer [1]
M 1: the number-average molecular weight of addition polymerization monomer [1]
For example, the two key concentration D about triethoxy hydroxymethyl-propane triacrylate can calculate in mode as follows.
D＝(3/428)＝0.00701
Even addition polymerization monomer [2], [3],, also use the method identical to calculate two key concentration D respectively with calculating formula a 2, D 3,, calculate two key concentration D of every 100g photoresist by calculating formula b T
D T＝(D 1×W 1+D 2×W 2+D 3×W 3··)×(100/W T)
(calculating formula b)
D T: two key concentration of every 100g photoresist
W 1: the quality (g) of the addition polymerization monomer [1] in the photoresist
W 2: the quality (g) of the addition polymerization monomer [2] in the photoresist
W 3: the quality (g) of the addition polymerization monomer [3] in the photoresist
W T: the gross mass of photoresist (g)
(C) composition can use known Photoepolymerizationinitiater initiater.Can use benzophenone derivates, benzyl ketals (べ Application ジ Le ケ one Le) derivative, thioxanthone derivates, Aryimidazole derivative etc.From the adhesiveness viewpoint, preferred 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer.The content of Photoepolymerizationinitiater initiater preferably contains 0.01～20 quality % with the gross mass benchmark of photoresist, more preferably 1～10 quality %.That is,, be preferably more than the 0.01 quality %, fully solidify, be preferably below the 20 quality % for the part at the end that makes photo-sensitive resin in order to obtain sufficient sensitivity.
From the fissility viewpoint, it is that 1000～3000 PPOX is as (D) composition that the photoresist among the present invention preferably contains weight average molecular weight.And then, from the viewpoint of the resolving power of fissility and resin mask, especially preferably contain weight average molecular weight and be 1500～2500 PPOX.From the viewpoint of fissility and resolving power, (D) composition preferably contains 7～30 quality % with the gross mass benchmark of photoresist.
In order to use above-mentioned dry film photoresist layer to form the resin mask layer, at first peel off protective film from the dry film photoresist layer, layered photosensitive-resin is connected to the surface of aforesaid substrate 1.Then, the mask that on the surface of the photo-sensitive resin except the part of electrode 2, superposes.Then, make the part exposure of electrode 2, peel off after the support film, use Na 2CO 3The aqueous solution etc. develop, and the part that can be formed on electrode 2 thus has the resin mask layer 4 of peristome.Because the internal diameter of peristome and the size or the number of the electrode 2 that spacing is used decide, so be not particularly limited.
The thickness of resin mask layer 4 can be than the height height of the scolding tin projection 6 that forms, also can be lower than it.Specifically, the gross thickness that the height of scolding tin projection 6 is added up with respect to the thickness of the thickness of resin mask layer 4 and scolder resist film 3 is its 0.05～3 times, is preferably 0.1～1.5 times.Usually the thickness of resin mask layer 4 is about 10～300 μ m, is preferably about 30～150 μ m.
As precipitation type scolding tin composition 5, for example can enumerate the precipitation type scolding tin composition that (a) contains the slaine of tin powder and lead, copper, silver etc., perhaps (b) contains the precipitation type scolding tin composition of at least a kind of selecting and at least a kind the complex compound of selecting from aryl phosphine class, alkylphosphines class and pyroles from tin powder and silver ion and copper ion.The slaine of above-mentioned (a) and complex compound (b) also can mix use.In the present invention, the lead-free unleaded precipitation type scolding tin composition of preferred especially use.Also have, when being called tin powder, except comprising the metallic tin powder, comprise that also Xi-the Yin of argentiferous for example is that the tin-copper of tin alloy powder or cupric is tin alloy powder etc.As above-mentioned slaine, can enumerate organic carboxylate, organic sulfenic acids salt etc.
The ratio of the above-mentioned tin powder in the above-mentioned composition and the salt of above-mentioned metal or complex compound (weight of tin powder: the salt of metal or the weight of complex compound) can be about 99: 1～50: 50, be preferably 97: 3～and about 60: 40.Also have, in the present invention, compare, more preferably use the complex compound of metal with the salt of metal.
In above-mentioned composition, except mentioned component, can also mixed flux composition or solvent.As the flux composition, can use the flux composition that is used for tin-lead system, Xi-Yin system, tin-soldering tin materials such as copper system usually, as solvent, as long as other composition in can dissolved composition and adjust viscosity or concentration just is not particularly limited.
The coating of above-mentioned scolding tin composition 5 on substrate 1 can be full coat, perhaps also can use the coating process (using mould printing) with metal mask and squeegee.The coating weight of scolding tin composition 5 can be according to the size or the suitably decision of height of the scolding tin projection 6 that forms.Specifically, as long as coating weight is determined to making the amount that the soldering alloy of separating out becomes to be needed.
After coating, the temperature heating with regulation is separated out the soldering alloy.At this moment, the wetability height between the copper of the soldering alloy of generation and formation electrode 2 forms scolding tin projection 6 so optionally adhere on the surface of this electrode 2.When particularly stating complex compound in the use, have and improve the optionally trend of electrode 2 to the surface.Thereby after heating, natural cooling substrate 1 washes away remaining alloying component etc. with solvent etc., can prevent residual soldering alloy beyond electrode 2 thus.
If consider the thermal endurance of circuit substrate etc., heating-up temperature can be preferably about 200～260 ℃ for more than 200 ℃.In addition,, can be about 30 seconds～10 minutes usually according to decision such as the composition of composition heating time, be preferably 1 minute～about 5 minutes.The processing (coating and heat treated) of separating out of soldering alloy can be divided into more than 2 times or 2 times and carry out.After the heating, natural cooling substrate 1 for residual soldering alloy beyond electrode 2 not, washes away remaining alloying component etc. with solvent etc.
After the heat treated, peel off and remove resin mask layer 4.For this reason, in the present invention,, use at least a kind of solvent from glycol ethers and alkamine, selecting as stripper.As glycol ethers, for example can enumerate the monoether class of glycol, two ethers of glycol, the ester class of glycol monoether etc.Wherein, the monoether class of preferred diol, the monoether class (carbitol class) of preferred especially diethylene glycol (DEG).
Monoether class as above-mentioned glycol, for example can enumerate glycol monoethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve), glycol monomethyl isopropyl ether (ispropyl cellosolve), ethylene glycol mono-n-butyl ether (butyl cellosolve), glycol monomethyl isobutyl ether (ethylene glycol monoisobutyl ether), glycol monomethyl uncle butyl ether (tert-butyl group cellosolve), ethylene glycol ether (hexyl cellosolve), diethylene glycol monomethyl ether (methyl carbitol), diethylene glycol monoethyl ether (carbitol), diglycol monotertiary isopropyl ether (isopropyl carbitol), diglycol monotertiary n-butyl ether (butyl carbitol), diglycol monotertiary isobutyl ether (isobutyl group carbitol), diglycol monotertiary uncle butyl ether (tert-butyl group carbitol), diglycol monotertiary hexyl ether (hexyl carbitol), propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, the propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPG list ether, DPG list positive propyl ether, the DPG mono-n-butyl ether, the tripropylene glycol monomethyl ether, 1,3-butanediol monomethyl ether (methoxybutanol), 3-methyl-methoxybutanol (ソ Le Off イ Star ト) etc.
As two ethers of above-mentioned glycol, for example can enumerate ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol (DEG) di-n-butyl ether, triethylene glycol dimethyl ether, many glycol dimethyl ethers, DPG dimethyl ether etc.
As the ester class of above-mentioned glycol monoether, for example can enumerate ethylene glycol monoethylether acetate (cellosolve acetate), ethylene glycol monomethyl ether acetate (butyl cellosolve acetate), diethylene glycol monoethyl ether acetic acid esters (carbitol acetate ester), diethylene glycol monobutyl ether acetic acid esters (acetate of butyl carbitol), propylene glycol methyl ether acetate, 3-methyl-methoxyl group butylacetic acid ester (ソ Le Off イ Star ト acetic acid esters) etc.
As alkamine (chain alcamines), for example can enumerate monoethanolamine (2-monoethanolamine, the 2-ethylaminoethanol), diethanol amine, triethanolamine, single Propanolamine, dipropanolamine, tripropanol amine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, only son's hydramine, two butanolamines, neopentyl alcohol amine, N, the N-dimethylethanolamine, N, the N-diethyl ethylene diamine, N, the N-dimethyl propanol amine, N, the N-diethylpropanolamine, N-(beta-aminoethyl) monoethanolamine, the N-methylethanolamine, N methyldiethanol amine, N-normal-butyl monoethanolamine, N-tert-butyl group monoethanolamine, N-tert-butyl group diethanol amine, N, N-di-n-butyl monoethanolamine, N-ehtylethanolamine etc., wherein, the preferred ethanolamines of using, preferred especially monoethanolamine.
Especially in the methods of the invention, the preferred at least a kind of solvent selecting from glycol ethers that uses is as stripper.This be because, compare with alkamine, glycol ethers is given the scolder resist of substrate or damage that scolding tin causes still less.
These solvents can use separately, and perhaps for example water, alcohol etc. mix use with other solvent.When with other solvent, at least a kind of solvent selecting from glycol ethers and alkamine can be preferably more than the 15 quality % for more than the 10 quality % with respect to the solvent total amount.
Removing of resin mask layer 4 is to be undertaken by the resin mask layer 4 that utilizes heat treated to form substrate 1 surface of scolding tin projection 6 is contacted with above-mentioned solvent.Contact method comprises the infusion process that for example substrate 1 be impregnated in the above-mentioned solvent, with solvent spray spray-on process on substrate 1 etc.In addition, the temperature of the solvent that uses is not particularly limited, can suitably selects from 1～80 ℃, preferred 15～65 ℃ scope usually.In addition, remove the 4 needed times of resin mask layer, be the time that resin mask layer 4 contacts with above-mentioned solvent can be about 30 seconds～2 hours, be preferably 50 seconds～45 minutes.Usually treatment temperature is high more then can shorten the processing time more.
In addition, also substrate 1 can be impregnated in and carry out ultrasonic waves for cleaning in the above-mentioned solvent.Like this, can further shorten the processing time.
The height of the scolding tin projection 6 among the present invention is generally 40～100 μ m.By the inventive method, can arrange this scolding tin projection 6 with narrow-pitch, the spacing about also can corresponding about 80 μ m.
Also have, in this embodiment, illustrate the substrate that electrode 2 (wiring layer) only is set on one side, the inventive method can be applied to be provided with the substrate of electrode (wiring layer) or too except also be provided with the substrate of electrode (wiring layer) with external inside at one or both sides on the two sides.Specifically, the inventive method except can be used for multichip module, by various encapsulation (package) to the formation of electrode (conductive pattern) to the projection of lip-deep pre-coated, combination (build-up) technology substrate is to beyond the formation of the preparation scolding tin of the through hole on the pad, fine pitch projection, also can be applied to TCP (Tape Carrier Package) carry with soldering-tin precoating apply, QFP (Quad FlatPackage) carries with big capacity pre-coated etc.In addition, in the so-called in the present invention insulating barrier, do not include only substrate, comprise the scolder resist film yet.
Below, the present invention will be described in more detail to enumerate embodiment, but the present invention is not limited by these embodiment.
Embodiment
Embodiment 1
(substrate)
As substrate, the surface is covered by the scolder resist film of thick 10 μ m, uses from the peristome (diameter: the substrate of exposed pad (non-electrolytic nickel gold plating electrode) 80 μ m) that is formed at this scolder resist film.Pad is to be formed on the substrate with 150 μ m spacings.
(dry film photoresist layer (a) makes)
Mix following composition and make photoresist solution.
Methyl methacrylate 65 weight %, methacrylic acid 25 weight %, butyl acrylate 10
The methyl ethyl ketone solution of the terpolymer of weight % (solid component concentration 34%, heavy
Average molecular weight 80,000, acid equivalent 340) 65g
Methyl methacrylate 65 weight %, methacrylic acid 25 weight %, butyl acrylate 10
The methyl ethyl ketone solution of the terpolymer of weight % (solid component concentration 34%, heavy
Average molecular weight 120,000, acid equivalent 340) 88g
Triethoxy hydroxymethyl-propane acrylate 10g
In addition on many propylene glycol of average 8 moles expoxy propane further respectively at two ends
The dimethylacrylate 7g of the glycol of the oxirane that addition is average 3 moles
To Nonylphenoxy seven ethyoxyl dipropoxy acrylate 5g
2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer 3g
4,4 '-two (diethylamino) benzophenone 0.14g
Diamond green 0.04g
Colourless (leuco) crystal violet 0.5g
Many propylene glycol (Japanese grease (strain) system ユ ニ is a Le D-2000) 10g
Para toluene sulfonamide 5g
Methyl ethyl ketone 10g
(the two key concentration D of the addition polymerization of every 100g photoresist T: 0.106)
Then, generate dry film photoresist layer (a) according to following step.
Use rod to be coated with machine and above-mentioned photoresist is coated on the pet film of thick 19 μ m the duplexer of be supported film and photoresist.Dry above-mentioned duplexer is 3 minutes under 90 ℃.Photosensitive resin coating and to make dried photoresist thickness be 38 μ m.With the photoresist face of support film opposition side on stacked protective film, obtain dry film photoresist layer (a).
(making of resin mask layer)
Peel off protective film from above-mentioned dry film photoresist layer (a), layered photosensitive-resin is connected to the aforesaid substrate surface, then, on the surface of photo-sensitive resin, dispose mask.Then, make each pad and exposure on every side thereof, peel off support film then, use Na 2CO 3The aqueous solution develops, and is formed on pad portion and has the resin mask layer of thickness 38 μ m that internal diameter is the peristome of 130 μ m with 150 μ m spacings.
(precipitation type scolding tin composition)
Mixing following composition obtains the scolding tin composition.
Sn/Pb alloy powder 75 quality %
(Sn/Pb=70/30, average grain diameter 10 μ m)
Lead naphthenate 10 quality %
Flux 15 quality %
The flux that uses is the composition that mixes following prescription, is cooled to the product of room temperature after making its heating and melting under 120 ℃.
Abietic resin 70 quality %
Hexyl carbitol (solvent) 25 quality %
Solidify castor oil (thixotropic agent) 5 quality %
(scolding tin is separated out processing)
By using mould printing, be filled in the above-mentioned scolding tin composition that obtains at each peristome of aforesaid substrate.Then, by heating more than 240 ℃ 1 minute, on each pad, form the scolding tin projection.(modulation of resin mask layer stripper)
2-ethanolamine solutions (gas chemical company of Mitsubishi system) 17ml and distilled water 83ml are mixed, modulation stripper 100ml.
(lift-off processing of resin mask layer)
In the 200ml beaker, add the stripper 100ml of above-mentioned modulation, be heated to after about 40 ℃, the aforesaid substrate that forms the scolding tin projection be impregnated in the stripper 1～2 minute, remove Ba Yan by hot plate.
Embodiment 2
Adding has been heated to about 60 ℃ butyl carbitol 1L in ultrasonic cleaning equipment, with the embodiment 1 the same substrate that floods the tape tree fat mask layer that has formed the scolding tin projection therein, carries out 3～5 minutes ultrasonic waves for cleaning, removes the resin mask layer.
Embodiment 3
The same with embodiment 1, the substrate that has formed the tape tree fat mask layer of scolding tin projection be impregnated in 20 ℃ in the stripper that embodiment 1 obtains 30 minutes, remove the resin mask layer.
Comparative example 1
The substrate of the tape tree fat mask layer that has formed the scolding tin projection that will obtain with the method identical with embodiment 1 impregnated in 40 ℃ the NaOH aqueous solution 2 minutes, removes the resin mask layer.
Comparative example 2
The substrate of the tape tree fat mask layer that has formed the scolding tin projection that will obtain with the method identical with embodiment 1 impregnated in 20 ℃ the NaOH aqueous solution 30 minutes, removes the resin mask layer.
To the scolding tin projection that in each embodiment, comparative example, obtains, carry out following evaluation.
(evaluation method)
1. the visual examination of scolder resist and resin mask layer residue has or not
Use microscope (キ one エ Application ス corporate system VH-6300), confirm that the resin mask layer has open resist change in color and have or not resin mask layer residue on the substrate resist after the resin mask layer lift-off processing before and after lift-off processing.Evaluation criterion is as follows.
The variable color of scolder resist: zero=no variable color, *=variable color arranged
Resin mask layer residue: zero=no residue, *=residue arranged
2. the visual examination of scolding tin projection
Use microscope (キ one エ Application ス corporate system VH-6300), shape, the gloss of each the scolding tin projection after the lift-off processing of affirmation weir, dam.
Evaluation criterion: zero=smooth surface and the hemispherical projection of scolding tin gloss is arranged
△=have from the teeth outwards is uneven or do not have the hemispherical prominent of scolding tin gloss
Rise
The oblate shape projection of *=do not have scolding tin gloss
3. the scolding tin zygosity of scolding tin projection
After the lift-off processing of weir, dam, on the scolding tin projection, be coated with flux, and then carry solder ball thereon, after heating more than 240 ℃ 1 minute, by microscope confirm solder ball whether with the scolding tin protrusion engagement.
Evaluation criterion: zero=engage well, *=engage bad
These result of the tests are shown in table 1.
Table 1
The variable color of scolder resist Resin mask layer residue The outward appearance of scolding tin projection The scolding tin zygosity
Embodiment
1 ○ ○ ○ ○
Embodiment 2 ○ ○ ○ ○
Embodiment 3 ○ ○ ○ ○
Comparative example 1 × × × ×
Comparative example 2 × × △ ×
As known from Table 1: compare as the comparative example of stripper with using strong base solution, embodiment causes damage seldom for scolder resist or scolding tin projection, also can not damage the scolding tin zygosity.

Claims (14)

1. the method for removing of a resin mask layer is characterized in that, comprising:
Use the dry film photoresist layer around electrode that the peristome from the insulating barrier that is formed at substrate surface exposes, to form the operation of resin mask layer,
The operation of coating precipitation type scolding tin composition on described substrate,
To this precipitation type scolding tin composition carry out heat treated and on described electrode surface, separate out scolding tin operation and
Remove the operation of described resin mask layer;
Removing of described resin mask layer after the heat treated can use at least a kind of selecting from glycol ethers and alkamine to carry out.
2. the method for removing of resin mask layer according to claim 1 is characterized in that,
The temperature of described heat treated is more than 200 ℃.
3. the method for removing of resin mask layer according to claim 1 is characterized in that,
In contain at least a kind the stripper of selecting from described glycol ethers and alkamine, dipping has formed the substrate of described resin mask layer, removes described resin mask layer.
4. the method for removing of resin mask layer according to claim 1 is characterized in that,
In contain at least a kind the stripper of selecting from described glycol ethers and alkamine, dipping has formed the substrate of described resin mask layer, carries out ultrasonic waves for cleaning.
5. the method for removing of resin mask layer according to claim 1 is characterized in that,
Described glycol ethers is the monoether class of glycol, and described alkamine is an ethanolamines.
6. the method for removing of resin mask layer according to claim 1 is characterized in that,
Described dry film photoresist layer is the stacked body of photoresist of stacked in order photo-sensitive resin and protective film on support film.
7. the method for removing of resin mask layer according to claim 6 is characterized in that, the operation that forms described resin mask layer comprises:
Peel protective film and layered photosensitive-resin is connected to the operation on the surface of described substrate from described dry film photoresist layer;
The operation of stack mask on the surface of the photo-sensitive resin except the part of electrode;
Make the operation of the part exposure of electrode; With
Peel described support film and develop and the part that is formed on electrode has the operation of the resin mask layer of peristome with developer solution.
8. the method for removing of resin mask layer according to claim 6 is characterized in that,
Described photoresist contains following forming, that is, (A1) weight average molecular weight be the alkali solubility macromolecule that contains carboxyl 15～35 quality %, (A2) weight average molecular weight of 40,000～90,000 be 100,000～150,000 the alkali solubility macromolecule that contains carboxyl 15～35 quality %, (B) addition polymerization monomer 15～60 quality %, (C) Photoepolymerizationinitiater initiater 0.01～10 quality % and (D) weight average molecular weight be 1000～3000 PPOX 7～30 quality %.
9. the method for removing of resin mask layer according to claim 1 is characterized in that,
With the two key concentration D of the addition polymerization of every 100g photoresist TBe that the photoresist below 0.12 is stacked on support film more than 0.07, use the dry film photoresist layer formation resin mask layer that protective film forms is set on the surface of this photo-sensitive resin.
10. the manufacture method of the substrate of a tape welding tin projection is characterized in that, comprising:
Use the dry film photoresist layer around the electrode of substrate surface, to form the operation of resin mask layer;
The operation of coating precipitation type scolding tin composition on described substrate;
This precipitation type scolding tin composition is carried out heat treated and on described electrode surface, separate out the operation of scolding tin projection; With
At least a kind of selecting from glycol ethers and alkamine of use is removed the operation of the described resin mask layer after the heat treated.
11. manufacture method according to claim 10 is characterized in that,
Described substrate is made of at least 1 wiring layer and 2 insulating barriers at least, and the vitrification point of at least 1 insulating barrier is than the temperature height of described heat treated.
12. manufacture method according to claim 11 is characterized in that,
The temperature of described heat treated is more than 200 ℃.
13. manufacture method according to claim 10 is characterized in that,
In contain at least a kind the stripper of selecting from described glycol ethers and alkamine, dipping has formed the substrate of described resin mask layer, removes described resin mask layer.
14. manufacture method according to claim 10 is characterized in that,
Described dry film photoresist layer is the stacked body of photoresist of stacked in order photo-sensitive resin and protective film on support film.
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